Manganese-(ii)salts of phosphonic acid half-esters

ABSTRACT

1. A COMPOUND OF FORMULA I   (R1-P(=O)(-O-R2)-O(-))X (A(-))Y MN(++)   WHEREIN R1 IS SELECTED FROM THE GROUP CONSISTING OF ALKYL WITH 1 TO 18 CARBON ATOMS, CYCLOHEXYL, ARYL WITH 6 TO 10 CARBON ATOMS WHICH IS UNSUBSTITUTED OR SUBSTITUTED BY 1 OR 2 METHYL GROUPS, AND ARALKYL WITH 7 TI 11 CARBON ATOMS, A$ IS SELECTED FROM THE GROUP CONSISTING OF AN ANION OF AN ALIPHATIC CARBOXYLIC ACID WITH 1 TO 18 CARBON ATOMS, AN ANION OF AN AROMATIC CARBOXYLIC ACID WITH 7 TO 11 CARBON ATOMS, AND THE CHLORIDE, BROMIDE, AND IODIDE ANION, X IS 1 OR 2, Y IS 0 OR 1, WITH X+Y BEING 2, AND R2 IS ALKYL WITH 1 TO 18 CARBON ATOMS.

United States Patent 3,839,380 MANGANESE-(II) SALTS 0F PHOSPHONIC ACID HALF-ESTERS Jean Rody, Basel, and Paul Moser, Riehen, Switzerland, assignors to Ciba-Geigy Corporation, Ardsley, N.Y. No Drawing. Filed Aug. 21, 1972, Ser. No. 282,636

Claims priority, application Switzerland, Sept. 30, 1971,

14,210/71 Int. Cl. C07f 13/00 US. Cl. 260-429 R 14 Claims ABSTRACT OF THE DISCLOSURE New manganese-(II) salts of phosphonic acid half-esters are used as stabilisers for polyamides. The new compounds are manufactured from the corresponding sodium salts of the phosphonic acid half-esters and a manganese- (II) salt.

The subject of the invention are new manganese-(II) salts of phosphonic acid half-esters, their manufacture, their use for protecting polyamides and, as an industrial product, the organic material protected, with the aid of these salts, against the harmful influence of light.

It is known to employ manganese salts as light stabilisers for polyamides, especially for polyamides delustred with titanium dioxide. The salts concerned are the salts of the divalent manganese cation with anions of organic acids, for example acetate, oxalate, lactate and benzoate. They are added to the carrier material together with acids of phosphorus, either in the form of the corresponding sodium salts or as free acids or as their esters, such as sodium hexametaphosphate, phosphorous acid, phenyl phosphonic acid or esters thereof, before, during or after the polymerisation or polycondensation. However, these light-stabilised mixtures suffer from the disadvantage that they can partially be eluted by aqueous media, which manifests itself in a decrease in the light protection action above all after dyeing thin polymer structures, for example fibres, in aqueous liquors. The same disadvantage is also shown by phosphorus-free polyamide fibres stabilised with manganese salts of organic acids, such as manganese acetate, alone.

It has now been found, surprisingly, that new compounds of the formula I in which R, denotes alkyl with l to 18 carbon atoms, cyclohexyl, aryl with 6 to carbon atoms which is unsubstituted or substituted by 1 or 2 methyl groups or aralkyl with 7 to 11 carbon atoms, A denotes the anion of an aliphatic carboxylic acid with 1 to 18 carbon atoms or of an aromatic carboxylic acid with 7 to 11 carbon atoms or the chloride, bromide or iodide anion, x denotes 1 or 2, y denotes 0 or 1, with x+y being 2, and R denotes alkyl with 1 to 18 carbon atoms, are very good light stabilisers for polyamides.

As compared to the previously known manganese salts or their mixtures with phosphorus compounds, the compounds according to the invention show a distinctly improved action as light stabilisers and'furthermore have the industrially desired advantage of a substantially lower ease of elution from the polyamide by aqueous media. As compared to other previously known light protection agents for polyamides from the series of the salts or complexes of hydroxybenzylphosphonic acid half-esters with various other metal ions, the compounds according to the invention show a far better light protection action andsubstantially more favourable colour properties.

3,839,380 Patented Oct. 1, 1974 R and R in the formula I denote, for example, methyl, ethyl, n-propyl, iso-propyl, butyl, pentyl, hexyl, octyl, iso-octyl, decyl, dodecyl, tetradecyl or octadecyl.

R is preferably alkyl with 1 to 12 carbon atoms and particularly preferably alkyl with 2 to 12 and with 3 to 12 carbon atoms.

R is preferably alkyl with 2-18 carbon atoms such as methyl, ethyl, propyl, butyl or octyl. Methyl, ethyl or butyl are particularly preferred.

Aryl in the formula I denotes, for example, phenyl or naphthyl and aralkyl can denote benzyl, 2-phenylethyl or naphthylmethyl.

The anion A in the formula I can be the anion of an aliphatic carboxylic acid with 1 to 18 carbon atoms, for example the anion of formic acid, acetic acid, propionic acid, butyric acid, 2-ethyl-hexanoic acid, lauric acid and stearic acid.

The anion A can, however, also be the anion of an aromatic carboxylic acid with 7 to 11 carbon atoms, for example the anion of benzoic acid, of a toluic acid, of phenylacetic acid or of butylbenzoic acid.

Anions of aliphatic carboxylic acids with 2 to 8 carbon atoms, for example the acetate ion, or anions of aromatic carboxylic acids with 7 or 8 carbon atoms, for example the benzoate ion, are preferred as A Possible carrier materials for the-new compounds are polyamides and copolyamides which are obtained by polymerisation of diamines and dicarboxylic acids and/or of aminocarboxylic acids or the corresponding lactams. The substrates can be in the form of filaments, bristles, films, injection-moulded articles and the like.

The compounds of the formula I are added to the carrier materials in an amount which corresponds to 1.0 to 500 p.p.m. of manganese, relative to the carrier material. Manganese additions of 10 to 200 ppm. relative to the carrier material are preferred, and those of 10 to 70 ppm. are particularly preferred.

The new compounds can be incorporated into the polyamides before, during or after polyconden-sation, optionally conjointly with further additives. Possible further additives are: pigments, mainly titanium dioxide in its two modifications rutile and anatase, in concentrations of 0.01-3.0%, but also coloured pigments such as sulphides, phthalocyanines, and perylene pigments; chain regulators, for example acetic acid and benzoic acid; phenolic antioxidants or amine antioxidants such as 1,3,5- trimethyl-2,4,6-tri-(3,5-di-tert.-butyl-4-hydroxy benzy1)- benzene, pentaerythritol-[3-(4-hydroxy-3,5-di-tert. butylphenyl)-propionic acidJ-tetraester, 1,6 hex-amethylene- [3-(4-hydroxy-3,5-di-tert.-butylphenyl) propionic acid]- diamide, 4,4'-butylidene-bis'(3 methyl 6 tert. butylphenol) and ditert.-octyl-diphenylamine; UV absorbers which are prefer-ably incorporated into the polymer after the p'olycondensation, for example 2-(2'-liydroxy-3',5'-ditertamyl-phenyl)-benzotriazole and 2-(2'-hydroxy 5'- methyl-phenyl)-benzotriazole; furtheradditives, such as antistatic agents and fiameproofing agents.

The new compounds can also be added to the finished polyamide before or during shaping, for example by sprinkling (dry blending) onto dried granules or by applying a solution of the compounds according to the invention, and optionally further additives, to the polyamide and subsequently evaporating the solvent.

Various processes are suitable for the manufacture of the compounds of the formula 1. Thus, for example, 1 or 2 mols of a compound of the formula II Rr-P 0N3 (II) 3 in which R and R have the meanings indicated under the formula I, can be reacted with 1 mol of a compound of the formula III 4 2, isolated as sodium salts, and 9.90 g. (0.05 mol) of manganese-(II) chloride tetrahydrate are dissolved in 400 ml. of boiling ethanol. Hereupon, sodium chloride pre- Mn++(A (III) cipitates and is filtered off. In the case of Example 3, the ter also partially precipitates I e d e manganese salt of the half es 21 313 has the meaning mdlcated un er th at the same time. Here, removal of the sodium chloride w'th the It is, however, also possible to react 2 mols of a phos- 1s dlspainsed with and the Process 15 hon.c acid half ester of the formula Ha suspension. The filtrate or the resulting suspension is p 1 evaporated to dryness and the residue is extracted with 0 ORI the solvents mentioned in Column 3. The evaporated extract 1s subsequently sub ected to the further purifica- OH (Ha) tion described in Column 4 and is thereafter dried for 8 hours at a temperature of 60 C. and a pressure of 11 wherein R and R have the meanings indicated under the mm. Hg. Following this instruction, the manganese-(II) formula I, with 1 mol of manganese-(II) carbonate or salts mentioned in Column 5 are obtained, the properties manganese-(II) hydroxide. of which are described in Columns 9 to 10.

TABLE I Content,

percent Melting Ex. Additional purification End product Colour point No. Starting product Extractant operation Mn (II)- P Mn Properties consistency C.)

1 Ethanol. Solution in methylene chlo- Bis-(O-ethylethyl 18.2 16.6 Water (c);ethanol Pale pink 79-80 1| ride and precipitationwith phosphonate). (c); ligroin (h). powder. 01H; IIONa ether.

OC2H| 2 CH 0 Chloroiorm Extraction with acetone Bis-(O-ethyl-isopropyl 17.4 15.3 Water (c); ethanol White 340 I ll phosphonate). (h); toluene (h). powder. CH-P--ON8 CH; CzH

. .do Extraction with absolute Bis-(O-n-butylcyelo- 13.2 11.2 Ethanol (c); chlo- Pale beige 250 ll ethanol. hexylphosphonate). reform (c); 1201- powder. P-ONa uene (h). H CtHI 1 The substance is soluble in (h=at the boil, c=at room temperature.

1 Decomposition.

Suitable solvents for these reactions are above all water, alcohols, especially methanol, ethanol and isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dioxane, tetrahydrofurane, acetonitrile and mixtures of these solvents.

Since the manganese-(II) ion is easily oxidised, the reactions are advantageously carried out in an inert gas atmosphere, which can consist, for example, of nitrogen.

Since the manufacturing processes described are equilibrium reactions, the compounds formed are often obtained as mixtures which in addition to the desired compounds of the formula I contain further compounds which are in equilibrium with these in the particular reaction medium.

Such mixtures obtained by the manufacturing processes described are also suitable for use as light stabilisers for polyamides.

The invention is described in more detail in the examples which follow.

EXAMPLES 1 TO 3 (COMPARE TABLE I) EXAMPLES 4 TO 10 (COMPARE TABLE II) 0.1 mol of the phosphonic acid half-esters of Column 2, isolated as sodium salts, are dissolved in the type and amount of solvent indicated in Column 3 and a solution of 10.2 g. (0.0515 mol) of manganese-(H) chloride tetrahydrate in 50 ml. of the same solvent is added dropwise at 25 to 30 C. The precipitate thereby produced is filtered oif and eluted with the solvent mentioned until no further chloride ions are detectable in the filtrate. (Example 5 behaves differently in this working-up stage. On adding the manganese salt, an emulsion precipitates instead of a solid precipitate, and this emulsion is extracted with ether. After drying this solution with sodium sulphate, the ether is evaporated off and the residue is further worked up as shown in the table.) The crude manganese- (II) salts isolated in this way are in some cases subjected to a further purification described in Column 4. Thereafter the products are dried for 8 hours at C. and a pressure of 11 mm. Hg. Following this instruction, the manganese-(II) salts mentioned in Column 5 are obtained, the properties of which are described in Columns 0.1 mol of the phosphonic acid half-esters of Column 60 6 to 10.

TABLE II Content, Melt- Solvent percent ing Ex. amount Additional purifl- End product Mn Colour eonpoint No Starting product in (1111.) cation operation (II)- P Mn Properties sisteney C.)

.... I? Water None.............. Bis-gol-eghyl-ln- 11.1 Dimeitdhygfgrm- Pale piink 0e yp osp oam e c ow er. C H11PONa note). chloroform (c). p

6 El) Water (300).. Extiactigngvith Bli-IgOI-IXIrbuItyIII-Z- 9.9 Cfilortitorm (e), White masa..

e arm a room e y exy 05- mu 0 CH|(CHz);CH-P=Na temperature. phonate). p g

TABLE II.-Continuod Contentt, 1 i

ercen e t n Ex. Solvent Additional purifi- End product Colour poin%; No. Starting product amountin (1111.) cation operation Mn (II) P Mn Properties consistency C.)

6 Water (70)... Recrystallisation BlS-(O-ethyl-n- 10.2 9.2 Water (h),ehloro- Pale pink 76-77 11 from ethanol. dodecylphosform powder. CuHz P ON a phonate). ligroin (h).

7 10% None Bis-(O-n-butyl- 6.65 Dimethylform- White 98-99 I] strength octadeoylamide (h), powder. CnHar-P-O Na ethanol phosphonate). ethanol (h),

(120). ligroln (h). CAHD 8 O do Bis-(O-n-octadecyl 6.3 Dimethylform- Pale pink 118-120 H strength phenyl ami e (h), powder. P-ONa ethanol phosphonate). toluene (c). 5 (150).

CiaHu 9 0 Water do Bis-(O-ethyl- 10.9 Dimethyliormdo 200-204 1]? (150). benzylphosphoamide (h). CHz- 0Na nate).

$C2Hs 10 Ethanol .do Bis-(O-ethyl-a- 11.1 10.0 do White 228-229 (47 naphthyl powder.

phosphonate).

i CHr-iF-ONB EXAMPLE 11 or 2 methyl groups, and aralkyl with 7 to 11 carbon 50 p.p.m. of Mn, as Mn phosphonate from Example 1, 2, 6, 8 or 9, are sprinkled dry onto dried polyamide-6 granules delustred with 1.8% of TiO (anatase) and the sprinkle-coated mixture was spun by means of extruders into 20 den. monofilaments which were subsequently stretched.

For the comparison formulation, the amount of Mn-II acetate corresponding to 50 p.p.m. of Mn was dissolved in water and this solution was uniformly dried onto highly delustred polyamide-6 granules (1.8% of TiO The dry sprinkle-coated mixture was then also spun by means of extruders to give den monofilaments which were stretched.

As a further comparison, 20 den. monofilament silk delustred with 1.8% of TiO but free of Mn, were also manufactured.

These 7 silk formulations were exposed on a white cardboard background, free of tension, in the Xenotest 450, and the mechanical strengths were determined after 500, 1,000, 1,500 and 2,000 hours exposure time. For the data obtained, see Table III.

TABLE III Percent residual tenacity after hours (hrs.)

500 1, 000 I, 500 2, 000 Exposure time (hrs.) (hrs.) (hrs.) (hrs.)

Additives:

. gigithout Mrf1 m...1:\i... 1 1. 20

. p.p.m. o as n p osp onate fromi Il]v}rampl1\ah1 h -l 1.. 90 80 70 60 3. 50 p.p.m.o n as up osp onate from Example 2 85 85 70 65 4. 50 p.p.m. of Mn as Mn phosphonate from Example 6 85 75 65 55 5. 50 p.p.m. of Mn as Mn phospho- 6 50nate iromflliilamplleisnilunfi..- 85 70 60 50 ..m.o nas np osp o- 11%; from Example 9 95 85 75 65 7. 50 p.p.m. of Mn as Mn-II acetate 80 65 40 We claim: 1. A compound of formula I 0 OR: Ri-i (A LM o (I) wherein R is selected from the group consisting of alkyl with 1 to 18 carbon atoms, cyclohexyl, aryl with 6 to 10 carbon atoms which is unsubstituted or substituted by 1 atoms;

A is selected from the group consisting of an anion of an aliphatic carboxylic acid with 1 to 18 carbon atoms, an anion of an aromatic carboxylic acid with 7 to 11 carbon atoms, and the chloride, bromide, and iodide anion;

x is 1 or 2,

y is 0 or 1, with x+y being 2, and

R is alkyl with 1 to 18 carbon atoms.

2. A compound of claim 1, wherein R is selected from the group consisting of alkyl with 1 to 18 carbon atoms, cyclohexyl, phenyl, benzyl and naphthylmethyl.

3. A compound of claim 1, wherein R is selected from the group consisting of alkyl with 1 to 12 carbon atoms, phenyl and benzyl.

4. A compound of claim 1, wherein R is selected from the group consisting of alkyl with 2 to 12 carbon atoms, phenyl and benzyl and R is alkyl with 2 to 18 carbon atoms.

5. A compound of claim 1, wherein R is selected from the group consisting of alkyl with 3 to 12 carbon atoms and benzyl.

6. A compound of claim 1, wherein A is selected from the group consisting of the anion of an aliphatic carboxylic acid with 2 to 8 carbon atoms, the anion of an aromatic carboxylic acid with 7 to 8 carbon atoms, the chloride, bromide and iodide anion and R is selected from the group consisting of methyl, ethyl, propyl, butyl and octyl.

7. A compound of claim 1, wherein A is selected from the group consisting of the anion of acetic acid, the anion of stearic acid, the chloride anion, and the iodide anion, and R is selected from the group consisting of methyl, ethyl and butyl.

8. A compound of claim 1, wherein x is 2 and y is 0.

9. Compound according to claim 1, of the formula CzHs-P Mn++ 2 10. Compound according to claim 1, of the formula CH3 0 00m.

CH-P or.

7. 11. Compound according to claim 1 of the formula 12. Compound according to claim 1, of the formula E/OC H [Q-,, l

13. Compound according to claim 1, of the formula 14. Compound according to claim 1, of the formula 0/0 CaHr m-g M...

8 References Cited UNITED STATES PATENTS 2,224,695 12/ 1940 Prutton 260429 R 2,329,707 9/1943 Farrington et a1. 260429 R 2,346,155 4/1944 Denison et a1. 260429 R 2,708,204 5/1955 Bell et a1. 260429 R 3,310,575 3/1967 Spivack 260429 R US. Cl. X.R. 26045.75 R 

1. A COMPOUND OF FORMULA I 